Bituminous composition



United States Patent 11 2,753,274 'BITUlVIlNQUS :GOMPOSI'IJON Mathew'L. Kalinowski, :GhicagmiLowell Ta Crews, :Home- W001i, and John A. Bolt, Chicago, -Ill., assignors to St ar Oi Co p ny Gh ca 1 11-, a ,corpor iomof In iana N nmwing- Applicati Ma Serial No. 220,324 16 Glaims. g(Cl.t 6-;27 3.)

The present invention is directed tto iimprovements tin bitumen compositions, and particularlytto improvements inzrnineral aggregate oa il'lggCDIllpOSltlOIlS,,and more'parti tularlyaelates to bitumen compositions Ihavingimproved adherence to damp orwetmineral aggregates.

Residual oils and/or bituminousrmaterials used in the preparation of pavements and roads do not ;,coat and adhere well to mineral aggregates :unless tthe aggregate is substantially dry, and for this reasonoin conventional pavements or road consrtuction practice, it :is customary to, dry the. mineral, aggregate bytsuitable well'known methods. Furthermore, water entering the ,road t or pavement during service may ,have ;a detrimental ef e t in that ;it may displace the oil or bitumen :from the surface of:the aggregate andthus diminish-,thegbonding etfecttofthetoil and/ or bitumen. This materially shortens thezlife of ,the road or pavement requiring-frequentrepairs andtis, therefore, uneconomical.

Mineral a r g tes employed in road o :p vernen tconstruction ,range in character from -hyidrophilic to :hydrophobic. In general, ,siliceous and acidic :minerals, such as sands and gravels, tend to be hydrophobic, awhile calcareous, salkaline minerals, such as limestone, "tend to be hydrophilic. It hasbeenobserved thatzthe mineral::age at appea have greate t r ction :.f r wat r than for oil orbitumens ,andthat ibis difficult yto obtain, y fi Y nalmethod s comp et lor ati facto y-floati f a eg t s by oil or t bitum n wh n w te .i presen 'Furthermore, even though;satisfactorytcoating is obtained y u ng d y a eg he LQ or abitum n tend to :b displaced if water enters the ,pavement tor read.

.It is known 1 thatthe; coating: of damp or wet .rnineral; aggregates by oil :or biturnen m y the efiected and {the resistance r of the coating ;t o displacement or stripping by water improved :by treating the aggregate with small amounts of ,a watersoluble soap ,of a fattyacid ginoonjunction with -a watensoluble salt of ,a polyvalent heavy metal or factivator? For optimum results with these reagents, the relative amounts of the two reagent-s -m ust be carefully adjusted. Thus, when a,di'valent heavy metal is sed as activa r, t e amoun o oap :Kuse sh uld be subs an ial y n mo wee l of ac vato w th trivalent metal, between one v and two rnolcs of t soap per mole of activator. Use of largenamounts of-soap than this diminishes the effectrobtained, and sthis diminution .ofetfect increases twithrexcess of soap over -thetpropor- .tions given until, twhenthe-amount of soap becomes equivalent to the activator, i. e -two molesof -soap;p,er;rn ole of .divalent metal -,or three per ,rnole of ,trivalent metal, the beneficial effect .of the reagent substantially disap- .Pear

The abovemethod has thedisadvantage that the relative amounts, of soap: and,polyvalent heavy-metal; activator: are cr t ca and m s th arefully adjuste fo optimum results. Use of an GXGflSS of :soap over the optimum amount diminishes ,rather than tenhances the eflect ob- .tained; the use of ,excessheavy;metahtoavoidthe danger of ,excess soap is not ,harmful but increases the .cost. Furthermore, :the two reagents must ,be weighed or measured ,out and ,added to ,each batch, ,as neither :is soluble ,in thao or b tumem-wh l his disad anta ay be ,partially overcome tunder favorable .conditions by using, in place of the soap, a fatty acid dissolved in the Z,753,Z 74 Patented July 3, 1956 #2 oil or bitumen, this expedient is eflective only :under favorable t conditions of low moisture content of the .aggregate, adequate randeefiicient r mixing, etc. tUnder conditions whichare notiat -a ll severe, such as appreciable amounts of watenand/ or facilities for only moderately efiicient mixing, ,f atty, acids appear not to be sufiiloiently soluble in water tovr each and reactlwithmhe heavy :metal ion-to the required textent and if ,addeddirectlyrto thc mixture or ,dissolved imtheoilor bitumen, ,are practically without-effect.

Another important disadvantage of the above method is that a heavy polyvalent metal salt must be used with the soap. Furthermore, it has been found that while some limestones appear capable of adsorbing or reacting with polyvalent heavy metal ions and accordingly ,respond to some degree to ,the above method, a,gr eat many others do not, and withrthesetittis difficultorimpossible to obtain a good coating by the above method. Also, since the foregoing method is not in generalisatis- :factory with limestone, a great many naturahmixedaggregates such as gravels containing both siliceousandcal- ,careous particles will have only a portion of theparticles coated.

In addition to the use ofpolyvalent fatty acid soapsin biturnens gas mineral aggregate coating agents, .certain organic nitrogen compounds, such as those obtained by reacting a polyamine with a fatty acid under conditions to form t essentially amides, have been used "for this ;purpose. However, although the amide-type ,asphalL-additives are effective, coating agents for acidicmineral tag- ,gregates, such ,as s ands and ,gravels, they are :inofiective on alkaline mineral aggregates, :Sllfih astlirnostone.

It ,is ,an object of the ,present invention to provide .a bituminous material ,having improved coating properties. It ,is also t an object of ,the present invetni'on itO provide an ,oil or bitumen composition which will adhere Ito ,wetted acidicand ,alkalinemineral aggregates. Another object of ,the presentinve ntion is to ,provide arcoating composition for acidic and alkaline mi eral aggregates which ,will not be stripped therefrom byaqueou s rliguids. Still another object of thetinvention isto provide a.co,ating composition ;for acidic {and alkaline mineralaggregates which n can ,be i applied without the necessity of drying the mineral aggregate and which ,will tadhere thereto .eyen in,a .wet condition. ,Ar other objectof the invention is ,tmprowide a method of preventing stripping of tlhe t coating composition from acidic and alkaline 'mineral aggregates by ,water after the road andflor pavement isconstructed. further object of the invention is to provide a method of ,promoting ,the adherence of .oil bituminous materials to siliceous and limestone aggregates without the necesy of d y t e s m Other obj ct an a an age oftthe'invention ,will becomeapparent as description thereof proceeds.

,In accordance with the present invention, bitumons, such ,as for example, ,roadtoils and asphalts having ,improved mineral aggregate coating, properties, especially with ,respeotto wet acidic and ,alkaline mineral aggregates, re t ine .by nsorpotatinglin su h bitumenstfromahout (1,25% toabout 5%, and preferably from about 0.5% to about 3%,, by volume, basedon the bitumen, of -the,oilsoluble produ t btained by reacting an aliphatic polya nine with the propane-insoluble fraction obtained in ,thepropane extraction of crude fatty materials, such as animal ,,marine and vegetable fats, fatty oils ,or fattytacids split therefrom, underconditions which avoid the formationof amidesso that a tproduct essentially freeof amido groups is obtained. .Since ,amidation .of amine soaps is brought about by "the loss .of .water at high temperatures, themeaction of the aliphatic polyamine with the aforementi ned :prqpaneain olubl tr ction is carri out at temperatures below about 265 F., preferably below 3 about 240 F., and more preferably at temperatures of from about 180 F. to about 225 F.

The propane-insoluble fraction obtained in the propane extraction of crude fatty materials of the type above described contains, in addition to fats and fatty acids, esters of fatty acids and sterols. These propane-insoluble fractions which are obtained as residue of the order of about 0.2% to about by weight, contain most of the color bodies which are present in the crude fatty materials, and because of their very dark color, are referred to in commerce as Ebony fats. The properties of representative samples of the propane insoluble residues obtained from animal fats and from vegetable oils, on a Water-free basis, are approximately as follows:

Residue Residue 1 Property from from Animal Vegetable Fat Oil Viscosity, Seconds Saybolt at 100 F 6, 500 930 Viscosity, Seconds Saybolt at 130 F 1, 860 430 Viscosity, Seconds Saybolt at 210 F 300 100 Ash, Weight "percent" 1. 3 .06 A. P. I. Gravity "degrees. 10 16 Acidity A. S. T. M. (D-664) Mg.KOH/gm 41 Pentane Insoluble, Weight "percent" 2. 6 4. 2 Benzene Insoluble, Weight percent .7 1.0 Saponification Number 190 170 Fatty Acid .r 20 31 Iodine Number 58 106 The above properties are, of course, merely illustrative, and it should be understood that both the amount and the property of the propane-insoluble residues depend upon the nature of the crude fatty material extracted, and upon the particular conditions employed in effecting the extracted fractionation. The term crude as used herein means that the color bodies and other materials, insoluble in 6 to 30 volumes of the propane at about 140 F. to about 190 F. have not been removed regardless of whether or not the fatty material has been destearinized.

The method of fractionating the animal, marine and vegetable fatty materials with propane to obtain Ebony fat is well known to those skilled in the art and one example thereof is commonly referred to as the Solexol process, currently and commercially used and described in Industrial and Engineering Chemistry of February ing acids split from such fats, the fractionation conditions i are employed which give a propane-insoluble residue of about 1%, i. e., about 0.2% to about 2%, although in some cases such residues may be as large as 5% or even 10%.

The amine reactant employed in preparing the additive of the present invention is an aliphatic polyamine, particularly an alkylene polyamine containing at least two primary amino nitrogen atoms. Examples of alkylene polyamines suitable for the herein-described purpose are ethylene diamine, propylene diamine, diethylene triarnine, diamylene triamine, triethylene tetramine, tripropylene tetramine, diethylenepropylene tetramine, tetraethylene pentamine, tetrabutylene pentamine, diethylenedipropylene pentamine, butylene diamine, dihexylene triamine, and the like, or mixtures thereof. For example, a suitable polyamine product is a crude diethylene triamine containing minor amounts of ethylene diamine and triethylene tetramine. Other suitable polyamines include those having the general formula RNH (CH2)3NH2 in which R is preferably a C10 to C18 aliphatic chain, and which are obtained by condensing the suitable amine with acrylonitrile and hydrogenating to the corresponding diamine. Commercially available polyamines of this type are those marketed by Armour and Company as Duomeens, which are prepared by the condensation of a dodecyl (Coco) amine or an octadecyl (tallow) amine 4 with acrylonitrile, followed by hydrogenation to the corresponding diamine product; these products are marketed as Duomeen C and Duomeen T, respectively.

In the preparation of the Ebony fat and polyamine reaction product, it is preferable, although not essential, that the Ebony fat be first dehydrated to obtain an essentially water-free product, or a product having not more than 0.5% water. This can be readily accomplished by diluting the Ebony fat with from about 10% to about 50% of a suitable hydrocarbon solvent, preferably a solvent rich in aromatic hydrocarbons, and by heating the diluted mixture at a temperature of about 210 F. to 290 F. while stirring and/or blowing with air or other suitable gaseous medium until the water content has been reduced to the desired value. If the Ebony fat contains an undesirable amount of contaminants, they can be removed by permitting the hot dehydrated solution to settle, and decanting the diluted solution of purified Ebony fat. If desired, the diluent may be removed from the dehydrated Ebony fat by suitable means, such as by distillation under vacuum; however, We prefer to react the diluted Ebony fat with the polyamine.

Aromatic-rich hydrocarbon solvents suitable for this purpose are preferably those having boiling points above about 220 F. at atmospheric pressure and includes mononuclear aromatic hydrocarbons or condensed ring aromatics, such as naphthalenes and mixtures of the higher boiling mono-nuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons.

A preferred source of mixed aromatic hydrocarbons suitable for the purpose, is a light catalytic cycle stock obtained from a powdered or a fluid-type catalytic-type hydrocarbon cracking operation in which gas oil or heavier hydrocarbons are cracked at a temperature of 800 F. to 1050 F., under a pressure of about atmos phere to 50 pounds per square inch, in the presence of suitable fluid or powdered catalyst, such as for example, silica-alumina, silica magnesia, and other well-known cracking catalysts. A method of conducting a fluidized cracking operation is described in U. S. 2,341,193 issued to Fred W. Scheineman, February 8, 1944. Fractions from the process heavier than gasoline, depending upon their boiling range, are commonly referred to as light catalytic cycle stock, heavy catalytic cycle stock and catalytic recycle resid, which usually are cycled to cracking. A light catalytic cycle stock particularly well suited as a diluent for the dehydration of the Ebony fat is a fraction having an aromatic content of at least about 40% and a distillation range between about 425 F. and about 560 F. A typical analysis of a suitable light catalytic cycle stock shows the material to be composed substantially of about 10% normal C12 to C20 parafiins, about 45% of other paraflins, and naphthenes, about 5% mono-nuclear aromatics, which are mainly monoto hexa-alkylated benzenes, and about 40% polynuclear aromatics, which are mainly alkyl naphthalenes, largely methylated naphthalenes. While we prefer to use a light catalytic cycle stock of the type described, hydrocarbon fractions from other catalytic conversion processes or thermal hydrocarbon conversion processes are suitable, provided they have an aromatic content of at least about 20%, and a distillation range of above about 220 F.

The dehydrated Ebony fat preferably, but not necessarily, in solution in the light catalytic cycle stock or other suitable diluent, is reacted with the polyamine in the ratio of from about 20:1 to about 5:1, and preferably in a ratio of from about 12:1 Ebony fat to the polyamine, at a temperature below about 265 F., and preferably of from about 180 F. to about 225 F., for not more than about one hour, and the temperature then reduced as rapidly as possible to about 170 F., or lower. By conducting the reaction in the manner herein described, and maintaining the finished product, until ready for use, at a temperature below about F., and prefis erably'below .about 140 F an ,e'fiicient stable coating agent. essentially. free. oftamido groups is obtained.

The preparation @Of ,polyarnine-Ebony 'fat reaction products .is illustrated "by [the following examples:

EXAMBLELI 161 pounds of Ebony fat;were mixed with "79 pounds of light CatalYIiC,CyClf-StOCk and dehydrated at atemperature f280F.to295F.-for about 'one' and threequarters hours while blowing'airthrough'the mixture. The temperature dfthe mixture was then-lowered to 210 F., 12 pounds of ethylene -tl iamine added, and the mixture-heated and cooled accordingto the following schedule .10 minutes at 210 .F. 1. .2.40 I); .lQmin tes at24. .F. to.2.6..0 E;

minutesat 26.0" F. to 265 E1; 20 minutes atf'26'5 and 25 minutes to cool from 2.65 f'F. to 175 F.

A .yield of about .248 upQtlndS of :the reaction .1 product i in light catalytic cycle stock solution containing about 66% of the active additive was obta e 4 EXAMPLE II 160; pounds 1 of .Ebony. tat was-mixed With-80 pounds .Qf light catalytic .cyclewstock-anddehydratedat 255 F. to 295 F. for; fourand one-ouarter hourswhile blowing air through the mixture. .To-the dehydrated Ebony fa were added pounds of triethylcne -tetramine (66%) .and the, mixture stirred at 240.F. to 265 F. for one hour. vThe temperature was then lowered to'220 F.

.for one'hour and thenrap idly reduced to175 F.

EXAM-BLEtIII 300 grams"of E-bonyfat, dehydratedeas in Example II, were reacted with 28 grams of tetraethylene pentamine at a temperature of about 225 F.- for about on hour, and then rapidly cooled to about 170 F. 1

EXAMPLE IV A dehydrated mixture of 300 gramsof .Ebonyfat in 150 grams light catalytic cycle stockwasreactedwith grams of propylene diarnine under conditions-given in Example III.

EXAMPLE V A solution of 2500 gallons of Ebony fat;in 2500 gallons of light catalytic cycle stock was heatedlo. about 240 F., and blown with air, for about-fourhours, until the water content was reduced to 0.15%. At,,a t emperature of 230 F., 300 gallons of tliethylene-tetramine were added, and the reaction was allowed to proceed for one-half hour. Cooling water was then turned ,on, the

mixture was cooled to 120 F., and .waslhen .pumped to finished additive storage.

EXAMPLE VI l00 .grams of Ebony .fa. and 120 grams of light catalytic cyclestock weremixed ,and"h eatedto 210 'F.-'-250 'F., while air blowing untibthemixturewas substantially anhydrous. Twenty grams of Duomeen 1T were added and heated at 230F. to -250F.-'for onehalf hour and then cooled.

EXAMPLE VII "The corresponding -reaetion product of -E,bony tat --and :Duomeen: C was prepared :.as -.;the;.corresponding Duomeen"T product in ExampleVI.

EEXAMBLE X A. solution of-3000 gallons. of Ebony fat; and 2000 gallons of light catalytic cycle. stock wasiheated to about 240 F.:and blown with air for about four hours to dehydrate the Ebony fat from a water content of 2.5% to a water content of 0.2%. To the dehydrated Ebony fat solution were added 225 gallons of ethylene paints, roofing materials, etc.

position may. be any bitumen which isusefulfor the coating of mineral aggregates usedlin themakingof roads, highways, etc., or for ,the .coating of other materials or surfaces where a twaterrresistant bondbetweenthesurface and the asphalt ,is advantageousor necessary. ,The term asphalt as ernployed herein is intended to-be synonymous with bitumen. andjtocover .a,,liq uid, semi-solid, or solid plastic bituminous material of the type employed in making or surfacing of-highways and/ or pavements, caulking agents, wsealing compounds, water impervious Such asphalt ;or bituminous materials are mixtures of hydrocarbons. ofnatural or pyrogenous origin, ,and .are usually derived, from petroleum or coalbut mayoccur as .such innature. As-

.phaltsmay be derived as distillationresids or cracking +resids withor without oxidationby air-blowing. or by catalytic oxidation. -A specific example of .a liquid .as-

pha lt of vthe. type, commonly employed. in the preparation of highways, etc. is a petroleum 1 residuum. :fluxed 'with a .light aromatic ,dilu entaboiling, in -.t he rangeof .400 F.

to 700 Fmto give ya cutback product of.the:following specifications:

Cutback asphalt Flash, -F. (T. 0.0;) NLT150 Viscosity, furolatal40aF -200 ASTM distillation:

Percent off at 4371F NMT 10.0 Percent oifat 5O0 F 15-55 Per cent ofl at 600 F 60.87 Residue at 680 F NLT 67.0 Tests on distillation:

Residue:

ASTM penetration at 77.F -300 ASTM 'ductility,at'77 F NLT 100 S01. inrCCLi, percent NLT 99:5 Oliensis spot test- .Negative 1 Not less than" Not more than Normally solid paving asphalts of the .40vlto'f200,penetration, grades commonly. used in road building falltwithin the following specifications:

Penetration at 7 7 F 40-200.

ASTM ductility at 77 F- r Not-less than 100. Oliensis spot test Negative.

Solubilityin CCl4, percent Not less than 99.5. Specific gravity at 60 F Not less than 0.990-1i000. Flash, F. (C. O. C.) Not less than 475.

.Loss on heating 50 grams for 5 hours at 325 F., percent- Not-more than025. Penetration of residue at 77 F., percent of original penetration -Not less than 70-75.

:The eiiectiveness of the herein-described Ebony Fatpolyarnine reaction productsin enhancing the adhesion .ofasphalts torwetwmineral aggregates is determined by subjecting;blends ofasphalts and the describedreaction products to one ;or more of 1 the following tests:

.A.. Modified Colorado. coating. tests zo rams.of;.Qttaw .s n WQIiZ stem -lo 312 1 35 mesh limestone are weighed into a 2 oz. container and covered with one-half inch of distilled water. One gram of the additive-containing asphalt is floated on the Water, the mixture then shaken for thirty seconds, and the extent of coating determined by visual inspection; the re- -8 A. Reaction production of Ebony fat and ene diamine prepared as in Example VIII.

B. Reaction product of -Ebony fat and diethylcne triamine prepared as in Example II.

ethylsults are expressed as Percent Coated. C. Reaction product of Ebony fat" and Duorneen B. Wyoming str pping test T i gg zi fi g'ti and Approximately 25 g. of Lander chips, all passing the meen C prepared as i E l V L inch sieve and retained on the No. 4 sieve, is mixed E Reaction product f Ebony fat d tetraethyp by hand with 1.0 g. of fortified asphalt until the be t ene entamine prepared as in Example III. possible coating is obtained. The mix is placed in an F, Reaction product of Ebony fat and propylene oven at 140 F. for 18 to 24 hours after which it is diamine prepared as i Example thoroughly remixed and is allowed to cool to room tem- G H and 3 Commercial asphalt coating perature. The sample is then immersed in distilled Water agents comprising essentially f tt acid polyamine at a temperature of 120 F., and is maintained at this i temperature for 3 Period of 24 h0uf5- At the and f The data in Table I demonstrate the effectiveness of this p h ih area offhe aggregate hemiflihihg Coatfid 15 the Ebony-fat-polyamine reaction product, prepared in determ ned visually while the sample s still under Water. Fhe manner hereimdgscribed, in maintailzling asphalt coat- Any thln or transl ucent areas are considered to be coated. mgs on both Wet acidic and alkaline mmeral aggregates, The WYmmg H1ghWaY P fl P Yeqmres that 80% The data with respect to additives and the n grfiatel coahhg he Ietamed thls testabove-described commercial asphalt coating agents, dem- C. H at settling test g nstirlate thiineifefcthl lfnless of theselproducts with respect 0 t 6 C021 mg 0 a alne mlnera aggregates, suc as 300 g j of i zi of g g gf limestone and/or the heat instability of such additives. i m c f? one K g i i fii th 25 The asphalt additives of the present invention exhibit or 9 i t t i g g Z exceptionally good stability with respect to resistance to f Eg 1S i z i Tho asy'halt coating degradation under typical storage temperatures Va i ess an 0 1S ere 6 1r o p ranging up to 170 F., as Well as under typical field apadditive mixture after being stored at 170 F. for the cation, mm eraturas of about 230 F 24-hour period is retested by the Colorado Coating Test p Th 1 t t f th h It d t (supra) for its ability to coat wet aggregates. e lea S 11 y 6 asp fi lrlves 6 The data obtained by subjecting blends of a cutback mmed by Stfmng alts contfmmg the addltlves of asphalt of the above specification and various Ebony Present omventlon glass Jars P of Fat-polyamine reaction products, prepared in the man- 77 140 and 170 F: for vallous Perlods 811d ner herein described, to one or more of the above-deteshng h Sample after Such test Perlods by the scribed tests are given in Table I. orado Coating Test (supra). For purposes of compari- TABLE I Colorado Coating Test Hot; Settling Test Wyoming Additive 1 Stripping Colorado Coating Sand, Limestone, Test, Sediment, percent percent percent percent Sand, Limestone, percent percent None (Control) C0ntroli1% Control-2 Control-4% B C0ntrol-2% B Contro1 C Contro1l% C. Control-%%D Control--%% D Contr0l -2% E. Control2% F Control--%% G- Control-4% G-.. Control-4% H. Control-2% Contro1--1%K.. Control+2% K In Table I the various additives are identified as folson, a commercial asphalt additive was subjected to the Additive GSame commercial asphalt additive as in Table I.

lows: same test. The results obtained are tabulated in Table II. TABLE II Storage Temperature 77 F. 140 F. 170 F.

Time (Days) 0 20 10 14 31 7 14 31 Percent Colorado Coating Sand Lime- Sand Lime- Sand Lime- Sand Lime- Sand Lime- Sand Lime- Sand Lime- Sand Lime- Sand Limestone stone stone stone stone stone stone stone stone pcrper- 1761- perperperperperpcrperperperperperperperperpercent cent cent cent cent cent cent cent cent cent cent cent cent cent cent cent cent cent Control (N o Additive) 0 0 0 0 0 0 0 O 0 0 0 0 0 0 0 0 0 0 Control+2% B. 100 95 100 95 100 95 100 95 100 90 80 90 90 70 90 C0nt1'0l+0.5% G- 0 90 O 90 0 5 0 5 0 Additive Same as in Table I.

Theheat stability of applicants asphalt additive under typical storage temperature conditions and its superiority over the commercial amide product 'are clearly demonstrated by the data in TableII.

10 to about 10% of the crude fatty material from which said insolublercsidue is extracted, said oil-soluble reaction product beingessentiallyfree ofamido groups.

2. A bitumen composition .as described in claim .1,

Since asphalts are applied at somewhat elevated temin which the alkylenepolyaminexis anallcylenepolyamme peratures up to about 230 F., it is important that such contalnlng at least two pfu y amluo b additive-containing asphalts show no degradation or loss A bltumen composltlon a descrlbed 1n c p m in efficiency at such temperatures. The heat stability of Which alkyleuo p y fu 15 all fy o u applicants herein described Ebony fat-polyamine re- A bluunon oomposluon o descrlbed f 1 111 action products at temperatures up to about 230 F., Whloh o alkylouo p y fu 1S y o l owhich is a typical temperatures at which asphalts are A bltumen p luon as descrlbed 1n cla1 m 1, in applied in road building or repair, is shown by the data Whloh o alkylene polyafume 1s dlethylenefirlammein Table iii. These data were obtained by storing ad- A bltumou oomposluou as fioscl'lbed 1n c1a1m ditive-containing asphalt samples at a temperature of alkylen? poly'fumm 1S a Polifamme mlxiure 230 F. for periods of time, and at stated intervals, testoomprlslllg essentlally d ethylene trramrne and minor ing such samples for their coating efficiency by the Coloamounts 9 ethylene m P and methylene tetramlne' rado Coating Test, and the Wyoming Stripping T A bitumen composition as described in claim 1, 1n (supra). The results obtained demonstrate that appli- Whlch alkylene 1S ma 1kyk1 1e tetbammeg cants additives are heat stable at temperatures as high A bltumen COmPOSmPH a diiscnbed m Clam} m as F for as long as fiftyflmr hours For C0mpara which the alkylene polyarnrne 1s tIICthYICHG tEtIaI HIIIC. tive purposes, an asphalt containing the commercial prod A bltumen P as descnbed clam uct, hereinabove described, was also tested under the Whlch the alkylene polyamme has the general formula: same conditions. RNH(CH2)3NH2 TABLE III Colorado Coating (Lander Chips) Wyoming Stripping Hours at 230 F 0 24 48 54 0 2c 48 54 Sand Lnne- Sand Lime- Sand Lime- Sand Limestone stone stone stone Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Control (No AdditiveL... 0 0 0 0 0 o 0 1o 10 10 10 Control+2.0% 100 85 95 85 95 85 90 85 95 95 85 70 Control+0.5% (3" 100 0 90 0 75 0 5 0 s5 80 30 Additive B-Same as in Table II.

Additive GSame as in Table II.

The data of Table III show the heat stability of the asin which R is an aliphatic group containing from about phalt additives of the herein described invention at typi- 10 to about 18 carbon atoms. cal application temperatures. The data also demonstrate 10. A bitumen composition as described in claim 1 the increased heat stability of the Ebony fat polyamine in which the crude fatty material is a crude animal fat. reaction products, essentially free of amides over that of 11. A bitumen composition as described in claim 1 a commercial product which is essentially an amide prodin which the crude fatty material is a crude vegetable oil. not. 12. A bitumen composition as described in claim 1 Although the Ebony fat-polyamine reaction products in which said oil-soluble reaction product is diluted with are heat stable at temperatures as high as 230 F., and from about 10% to about of an aromatic-rich hyexhibit essentially no degradation with respect to coatdrocarbon diluent having a boiling point above 220 F. ing and stripping efficiency, it is advisable to limit the 50 13. A bitumen composition as described in claim 1 blending and/ or storage temperature for the fortified asin Which the bitumen is a normally liquid bitumen, phalts to temperatures not in excess of about 150 F., A bitumen composition as described in claim 1 and preferably at temperatures not in excess of 140 F. in Which the bitumen is a normally solid paving asphalt. Likewise, asphalts containing the herein-described asphalt 5- A ro dway construction material resistant to water additives should preferably be applied at temperatures pp g comprising mineral aggregates admixed with a ot to exceed b ut 230 F, coating composition comprising a major proportion of a While the present invention has been described by refnormally liquid bitumen and from about 025% to about erence to specific embodiments thereof, these are given 5% of Tho oilrsolublo reaction Produot of an ulkylouo by way of illustration only, and the invention is not to be polyamine, having from 2 to about 20 Carbon atoms, and limited thereto but includes within its scope such modiy Which Ebony is the pfopauo-iusolublo fications and variations as come within the spirit of the residue obtained in The Solvent raCfiOn Of a crude appended claims. fatty material selected from the class consisting of crude w l i animal fats, fatty oils, and fatty acids, crude vegetable 1. A bitumen composition comprising a major proporfats, fatty oils, and fatty acids, and IniXtufbS thereof, With tion of bitumen from about 0.25% to about 5% of the oilliquefied Propane, Said insoluble residue being insoluble soluble reaction product of an alkylene polyamine, havill 6 to 30 Volumes of P p at temperatures of from ing from 2 to about 20 carbon atoms, and Ebony fat about to about and constituting from which Ebony fat is the propane-insoluble residue obabout 02% to about 10% of the Crude fatty material tained in the solvent extraction of a crude fatty material r In W h Said insoluble residue is eXtfabfod, Said selected from the class consisting of crude animal fats, soluble reaction product being essentially free of amido fatty oils, and fatty acids, crude vegetable fats, fatty oils, groups. and fatty aoids and mixfures b f With qu P 16. A composition described in claim 1.5 in which the pane, said insoluble residue being lnsoluble 1n 6 to 30 normally liquid bitumen is a petroleum residumn volumes of propane at a temperature of from about F. to about F. and constituting from about 0.2% 76 (References on following page) 11 References Cited in the file of this patent 2,534,713 UNITED STATES PATENTS 25425982 2,329,889 Ewing Sept. 21, 1943 2,383,097 Watman Aug. 21, 1945 2,436,599 Read et'al Feb. 24, 1948 151,666

12 Hankins Dec. 19, 1950 Bartleson et a1 Feb. 27, 1951 FOREIGN PATENTS Great Britain Oct. 7, 192,0 

1. A BITUMEN COMPOSITION COMPRISING A MAJOR PROPORTION OF BITUMEN FROM ABOUT 0.25% TO ABOUT 5% OF THE OILSOLUBLE REACTION PRODUCT OF AN ALKYLENE POLYAMINE HAVING FROM 2 TO ABOUT 20 CARBON ATOMS, AND "EBONY FAT" WHICH "EBONY FAT" IS THE PROPANE-INSOLUBLE RESIDUE OBTAINED IN THE SOLVENT EXTRACTION OF A CRUDE FATTY MATERIAL SELECTED FROM THE CLASS CONSISTING OF CRUDE ANIMAL FATS, FATTY OILS, AND FATTY ACIDS, CRUDE VEGETABLE FATS, FATTY OILS, AND FATTY ACIDS AND MIXTURES THEREOF, WITH LIQUEFIED PROPANE, SAID INSOLUBLE RESIDUE BEING INSOLUBLE IN 6 TO 30 VOLUMES OF PROPANE AT A TEMPERATURE OF FROM ABOUT 140* F. TO ABOUT 190* F. AND CONSTITUTING FROM ABOUT 0.2% TO ABOUT 10% OF THE CRUDE FATTY MATERIAL FROM WHICH SAID INSOLUBLE RESIDUE IS EXTRACTED, SAID OIL-SOLUBLE REACTION PRODUCT BEING ESSENTIALLY FREE OF AMIDO GROUPS. 